Lubricant



UNITED 's'r 'ras PAT-TENT: OFFICE.

LUBRICANT Bernard H. Shoemaker and Clarence M.-Loane,

Hammond, Ind., asslgnors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Application December 5. 1936, Serial No. 114334 V This invention relates to lubricants and in or tour nitrogen atoms only in the ring such as: particular, to "addition agents imparting improved pyrazole 1.2-diazo1e or pyrro (a) monazole) glyproperties to lubricants. oxaline or imidazcl (1.3-diazo1e), 1,2,4-triazole This invention has particular utility in im- (pyrro (abi) diazole), 1,3,4-triazole (pyrro (bbi) proving the lubricating properties of lubricating diazole), 1 2,3-triazole (pyrro (ab) diazole), 1,2,5- 6 oils and/or in preventing or inhibiting the corrotriazole .(pyrro (aai) diazole) 1,2,3;4-tetrazole sion of hard metal" alloy bearings such as cop- (pyrro (abbi) triazole), 1,2,3,5-tetrazole (pyrro. per-lead, cadmiumnickel and cadmium-silver (abai) triazoie); and the hereinbefore mentioned bearings which, we large extent, have replaced substituted derivatives in which the following 10 soft metal bearings, such as Babbitt metal, in numbering system is used; the trend toward internal combustion engines (3)) (2)).

having high compression ratios and increased! I acceleration and increased speed characteristics. The use oiXthe hard metal" bearings has crc- )01) (5)0 0 ted ubr eet n Corrosion Problems, D Examples of the substituted derivatives of the 15 40 alloy bearings can' be inhibited and highly del y in connection with highly refined 0115, o above are: n-octyl pyrazoles, phenyl pyrazoles, of which may be Ve y corrosive t0 bearings of phenyl dimethyl pyrazoles, di, tri and/or tetra the hard metal type. methyl pyrazoles, chlor pyrazoles, amino py- 7 .As used herein y fi i ng oil razoles, amino trimethyl pyrazoles, phenyl ethoxy means viscous o ls wh c v 8 minimum pyrazoles, methyl glyoxalines, phenyl glyoxalines, e-OSity of S- A 10 Oils d Oils having higher 4 5-methyl phenyl glyoxalines, chloro methyl viscosities, and which have been subjected to glyoxalihs, 4,5 diphenylgly0xa1lne-2-mercaptan, such refining processes that the paraflinicity of 5- 1111 eth l glyoxaline, phenyl 1,2,5-triaz0les, the oil is markedly increased. It has been found phenyl methyl ama-1 1. a i -1,2,5-t iv that highly refined lubricating oils cause corazoles, phenyl 1 2 3-t 1 h 1 ethoxy 1,2,3- 25 rosion t0 al y bearings the d mete-1 p triazoles, phenyl amino 1,2.3-triazoles, amino such as cadmium-Silver a oy e s t e X- methyl 1,2,3-triazoles, methyl 1,2,4-triazoles, tent of about 5 mg/cm. and even greater Wilen phenyl 1,3,4-triazoles, l-phenyl 1,2,3,4-tetrazole, such bearings are submerged for 25 hours orless l-methyl 1,2 3,4..1; 1; 1 i-phenyl-z methyl n a air agitated Oil Which has been DI'eOXidiZed 1,2 3,4-tetrazole, mercapto tetrazoles, amino tetat about 340 F. for 25 to 50 hours. The motor razoles, o ls h y b y refined lubricating 011$ The term azine as used herein comprises the such or mixtures of g y refined lubricating Oils hexa-heterocyclic compounds having two or more with, less highly refined lubricating oils, or stated nitrogen atoms only in t g c in another way, mixtures of corrosive oils and ridazine (1,2-diazine or orthadiazine), pyrimi- 35 non-corrosive oils, examples of the latter bein dine (1,3-diazine or metadiazine), pyrazine (1,4- lubl'ieating Oil fractions from w elude diazine or paradiazine), as-triazine (1,2,4-tricrudes 0f the W k tyD azine), s-triazin'e (1,3,5-triazine or .cyanidine), We have found that eorroswn of hard metal v-t-riazine (1,2,3-triazine), s-tetrazine (1,2,45-

tetrazine), v-tetrazine 1 2,3,4-tetrazine); and 40 simble properties can be imparted to lubrlceiing the hereinbefore mentioned substituted derivaoils by adding thereto up to 5%, but preferab tives in which the following numbering system 0.05% to 0.75%, oi a poly membered heterocyclic is used: e

compound having the general formula A-R in m which A represents a heterocyclic radical selected N 46 from the group consisting of azoles containing (6) (2) only nitrogen and carbon in the ring, azines containing only nitrogen and carbon in the ring, (5) (3) pyrroles and thiophenes, and R. represents hy- (4) 0 'drogen or a substituted radical or radicals, such v 50 as alkyl or aryl or aralkyl or alkoxy or mercapto Examples of derivatives of the above named or amino or substituted amino or halogenand/or compounds methyl p d zm pheny mix ures-thereon pyridazines, methyl phenyl pyridazines, methyl The term azole as used herein comprises the pyrimidines, methyl ethyl pyrimidines methyl penta heterocyclic compounds having two, three phenyl pyrimidines, dimethyl amino pyr midines, 55

engines.

amino pyrimidines, chloro dimethyl pyrimidines, 2,4,5,6-tetra chloro pyrimidine, methyl pyrazlnes, diphenyl pyrazines,'diphenyl methyl cyanidines, diphenyl cyanidines, triphenyl cyanidines, trimcthy] cyanidines, tributoxy cyanidines, chloro trimethyl cyanidines, amino cyanidines, diphenyl 1,2,3,4-tetrazine.

The term pyrrole as used herein, comprises the penta heterocyclic compounds having a 4 membered carbon chain united to a ring by a bivalent imino (NH=) group (sometimes called the imine group) and the hereinbefore mentioned substituted derivatives thereof such as: methyl pyrroles, ethyl pyrroles, isoamyl pyrroles, phenyl pyrroles, methyl phenyl pyrroles.

The term thiophenes as used herein comprises the penta heterocyclic compounds having only sulfur and carbon in the ring of the general structural formula Y (i) and the hercinbefore mentioned substituted derivatives thereof, such as: lauryl thiophenes, dicyclohexyl thiophenes, isopropyl thiophenes, hexyl thiophenes, phenyl thiophenes, diphenyl thiophenes, tetraphenyl thiophenes, methyl plienyl thiophenes, aminothiophenes, thiophthens (bithiophenes).

In addition to the hereinbefore mentioned types of compounds we may use other compounds closely related to the foregoing such as pyridine,'quinoline, brucine, thienyls such as dithienylmethane, thienyltriphenylmethane, and the like.

The effectiveness of these compounds as cori'osion inhibitors is demonstrated by the following test in which the inhibitor was subjected to conditions more severe than those encountered in the actual operation of internal combustion In this test weighed cadmium-silver alloy hearings were placed in containers containing a highly refined oil with and without the addition of the inhibitors and the oil air agitated and maintained at a temperature of about 341 F. At periodic intervals the bearings were removed from the oil baths, washed free 0? the oil and the loss in weight determined. Before being replaced in the oil-bath the bearings were polished bright, reweighed and again tested for predetermined periods. In this test the oil used was a 'motor oil refined to such an extent that a loss in weight of more than 5 ing/cm. is obtained in 25 hours or less on a cadmium-silver alloy bearing submerged in the air agitated oil at about 341 R, which oil had been preoxidized for 25 to 50 hours at about 341 F.

' In the table below are tabulated the results obtained in the above test using tributoxy cyanidine (1,3,5-triazine) as the inhibitor.

Loss in weight (mg/cm?) Periods Oil 1st, 24 2nd, 6 3rd, 16 hrs. hrs. hrs.

Control. 3. 59 5. 06 20. 5 Control-+02% tributoxy cyanidine 0. 24 0.00 0. 11

The above data illustrates the high inhibiting power of compounds of the type hereinbefore described.

chlorothiophenes, diamyl such as aluminum naphthenate, aluminum stearate and the like.

We do not wish to limit ourselves to the specific embodiments of our invention herein described except as defined by the app nded claims.

We claim 1. A motor oil non-corrosive to hard metal alloy bearings having the corrosive susceptibility of alloys of the class consisting of cadmiumsilver, cadmium-nickel, copper-lead alloys consisting of a mineral lubricating oil normally corrosive to said hard metal alloys and a small amount of a polymembered heterocyclic compound having the general formula A-R in which A represents a heterocyclic radical selected from the group consisting of azoles, containing only nitrogen and carbon in the ring, azines, containing only nitrogen and carbon in the ring, pyrroles and thiophenes and R is a substituent selected from the group consisting of hydrogen, an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, a mercapto radical, an amino radical, a substituted amino radical and a halogen, said polymembered heterocyclic compound being added in small butsuflicient quantities to inhibit the corrosion of said hard metal alloy bearings.

2. A motor oil non-corrosive to hard metal alloy bearings having the corrosive susceptibility of alloys of the class consisting of cadmium silver, cadmium-nickel and copper-lead alloys consisting of a mineral lubricating oil normally corrosive to said bearings and a' polymembered heterocyclic compound having the general formula AR in which -A represents an azole containing only nitrogen and carbon in the ring and R is a substituent selected from the group consisting of hydrogen, an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, a

mercapto radical, an amino radical, a substituted mino radical and a halogen, said polymembered heterocyclic compound being added in small but suflicient quantities to inhibit the corrosion of said hard metal alloy bearings.

3. A motor oil non-corrosive to hard metal alloy bearings having the corrosive susceptibility of alloys of the class consisting of cadmium-silver, cadmium-nickel and copper-lead alloys consisting of a mineral lubricating oil normally corrosive to said bearings and a polymembered heterocyclic compound having the general formula A-R'in which A represents an azine containing only nitrogen and carbon in the ring and R is a substituent selected from the group consisting of hydrogen, an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, a mercapto radical, an amino radical, a substituted amino radical and a halogen, said polymembered heterocyclic compound being added in small but sufiicient quantities to inhibit the corrosion of said hard metal alloy bearings.

4. A motor oil non-corrosive to hard metal alloybearings having the corrosive susceptibility of alloys of the class consisting of cadmiumsilver, cadmium-nickel and copper-lead alloys consisting of a mineral lubricating oil normally corrosive to said bearings and a polymembered heterocyclic compound having the general formula A-R in which A represents a thiophene containing only nitrogen and carbon in the ring and R. is a substituent selected from the group consisting of hydrogen, an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, a mercapto radical, an amino radical, a substituted amino radical and a halogen, said polymembered heterocyclic compound being added in small but sufiicient quantities to inhibit the corrosion of said hard metal alloy bearings.

5. A motor oil non-corrosive to hard metal alloy bearings having corrosive susceptibility of alloys of the class consisting of cadmium-silver, cadmium-nickel and copper-lead alloys consisting of a mineral lubricating oil normally corrosive to said bearings and tributoxy cyanidine, said tributoxy cyanidine being used in small but sufficient quantities to inhibit the corrosion of said hard metal alloy bearings.

6. A motor oil non-corrosive to hard metal alloy bearings having corrosive susceptibility of alloys of the class consisting of cadmium-silver, cadmium-nickel and copper-lead alloys consisting of a mineral lubricating oil normally corrosive to said bearings and hexyl thiophene, said hexyl thiophene being used in small but sufficient quantities to inhibit the corrosion of said hard metal alloy bearings.

7. The method of preventing corrosion of bearing metal alloys having the corrosive susceptibility of alloys of the class consisting of cadmiumsilver alloys, cadmium-nickel alloys, copper-lead alloys in the presence of highly refined lubricating oils in internal combustion engines which comprises adding to said lubricating oil from about 0.05% to about of a polymembered heterocyclic compound having the general formula A-R. in which A represents a heterocyclic radical selected from the group consisting of azoles containing only nitrogen and carbon in the ring, azines containing only nitrogen and carbon in the ring, pyrroles and thiophenes and R is a. substituent selected from the group consisting of hydrogen, an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, a mercapto radical, an amino radical, a substituted mino radical and a. halogen.

8. The method of preventing corrosion of hearing metal alloys having the corrosive susceptibility of alloys 01' the class consisting of cad- CERTIFICATE OF Patent No. 2,160,295.

e 3 mium-silver alloys, cadmium-nickel alloys, copper-lead alloys in the presence of highly refined lubricating oils in internal combustion engines which comprises adding from about 0.05% to about 5% of a polymembered heterocyclic compound having the general formula A-R. in which A represents an azole containing only nitrogen and carbon in the ring and R is a substituent selected from the group consisting of hydrogen, an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, a mercapto radical, an amino radical, a substituted amino radical and a halogen.

9. The method of preventing corrosion of bearing metal alloys having the corrosive susceptibility of alloys of the class consisting of cadmium-silver alloys, cadmium-nickel alloys, and copper-lead alloys in the presence of highly refined lubricating oils in internal combustion engines which comprises adding to said lubricating oil from about 0.05% to about 5% of a polymembered heterocyclic compound having the general formula AR in which A represents azines containing only nitrogen and carbon in the ring and in which R is a substituent selected from the group consisting of hydrogen, an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, a mercapto radical, an amino radical, a substituted amino radical and a halogen.

10. The method of preventing corrosion of bearing metal alloys having the corrosive susceptibility of alloys of the class consisting of cadmium-silver alloys, cadmium-nickel alloys and copper-lead alloys in the presence of highly refined lubricating oils in internal combustion en:

gines which comprises adding to said lubricating oil from about 0.05% to about 5% of a polymembered heterocyclic compound having the general formula A-R in which A represents thiophenes and R is a substituent selected from the group consisting of hydrogen, an alkyl radical, an aryl radical, an aralkyl radical, an alkoxy radical, a mercapto radical, an amino radical, a substituted amino radical and a halogen.

BERNARD H. SHQEMAKER. CLARENCE M. LOANE.

CORRECTION. I

May 50, 1939.

BERNARD H. SHOEHAKER, El AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correctionos follows: Page 2, secondcolumn, line 1 .6, claim 2, for "mino" read amino; and that the said Letters Patent should be read with this correction therein that the some may conform to the record of the case in the Patent Office. I

Signed and seale'dthis 25th day or July A. n. 1939. I

(Seal) soda-y Van Arsdale, Acting (lomnisaioner of Patents. 

